Certain subresinous esterification derivatives of acylated polyamines and method of making same



Patented Aug. 7, 1945 CERTAIN DERIVATIVES CF AC 7 AND METHOD or sunaasmows cs'ranmco g G SE Melvin De Groote, University City, and iliiiemlirard Keiser,

Webster Groves, Petrolite Corporation, Ltd, W w corporation of Delaware gners to r r Bet, a

No Drawing. Original application June 15, 1942, Serial No. 447,162. Divided and this applica tion August 2, 1943, Serial No. 491,122?

10 Claims.

This invention relates to a new chemical product or composition of matter, our present application beinga, division of our co-pending application Serial No. 447,162, flled June 15, 1942,

which subsequently issued as U. S. Patent No.

2,353,705, dated July 18, 1944.

The main object of our invention is to provide a new chemical product or compound that is particularly adapted for use as a demulsifier in the resolution of crude oil emulsions.

Another object of our invention is to provide a practicable method for manufacturing said new chemical product or compound.

Although one of theprimary objects of our invention is to provide a new compound or composition of matter that is an eflicient demulsifler for crude oil emulsions of the water-in-oil type, the said compound or composition of matter is adapted for use in other arts as hereinafter indicated.

We have discovered that if one oxyalkylatcs 1 glycerol so as to introduce at least three oxyalkylene radicals for each hydroxyl group, and

Y if the product so obtained is reacted with a polybasic carboxy acid having not over eight carbon atoms, and in such a manner as to yield a frac- 'tional ester, due to the presence of at least one free carboxyl radical, one can then esterify said acidic material or intermediate product with at least one mole of an alcoholic compound of the type herein described to give a variety of new compositions of matter which have utility in various arts, and particularly in the demulsiflcation of crude oil.

The compounds herein contemplated may be produced in any suitable-manner, but are usually ,manufactured by following one of two general procedures. In one of said procedures the oxyalkylated glycerol, which is, in essence, a polyhydric alcohol, is reacted with a polybasic acid so as to give an acidic material or intermediate product, which, in turn, is reacted with an alcoholic body of the kind hereinafter described,

and momentarily indicated by the formula' R1(OH)m. Genetically, the alcoholic body herein contemplated may be considered a member of the class in which 11!. may vary from 1 to 10,

although the specific significance of m in the present instance will be hereinafter indicated. The second procedure is to react an alcohol of the formula type R1(OH)m with a'polybasic acid so as to produce an intermediate product, and then react saidintermediate product or fractional ester with the selected oxyalkylate glycerol.

Glycerol may be conveniently indicated by the following formula:

Calls-0H If treated with an oxyalkylating agent, and momentarily, consideration will be limited to an oxyethylating agent, one may obtain an oxyethylated glycerol of the following formula;

mula: I

COOH

RZOOOH coon I then the acyclic reaction product of one mole of oxyethylated glycerol and one mole of a polybasic carboxy acid may be indicated by the following formula:

( z i )n' in which n" has the value of one or two. Sim= ilarly, if two moles of the polybasic acid be used,

then the compound may be indicated by the following formula: I

oramr-(cmiowooomooomw (C2Hlo) 'H If a fractional ester of the kind exemplified by the three preceding formulae is reacted with one or more moles of an alcohol of the kind previously described is a generic sense as R 1(OH) 1n,

then obviously, one may obtain a material of the type indicated by the following formula:

in which a: is 0, 1 or 2,1! is 0, 1 or 2, and z is 1, 2 or 3, and :c' is or 1, and y is l or 2.

It has been previously stated that compounds of the type herein contemplated may be obtained by oxyalkylating agents, without being limited to ethylene oxide. Suitable oxyalkylating agents include ethylene oxide, propylene oxide, butylene oxide and glycid, which, although not included, strictly speaking, by the unitary structure CnH2n0, is included within the meaning of the hereto appended claims and may be simply considered as a variant of propylene oxide, i. e., hydroxypropylene oxide. Similarly, where a carboxylic hydrogen atom appears, it may be replaced by metal; an ammonium radical, or substituted ammonium radical, or by an organic group derived from an alcohol, such as an ali-' phatic alcohol, an aralkyl alcohol, or an alicyclic alcohol. It may also be converted into an amide, including a polyamino amide. ceding formula may be rewritten in its broader scope, as follows:

in which n replaces the numbers 2, 3 or 4, z includes the acidic hydrogen atom itself. In the above formula, and hereafter-for convenience,

R1 is intended to include any hydroxyl groups that remain.

If the compounds herein contemplated are obtained under usual conditions, at the lowest temperatures, then the monomeric form is most likely to result.

The production of the compounds herein con- V templated is the result of one or more esterificalike. Another and better procedure, in many in-' stances, is to employ the vapors of .a suitable liquid, so as to remove any water formed and condense both the vapors of the liquid employed and the water in such a manner as to trap out the water and return the liquid to the reacting vessel. .This procedure is commonly employed in the arts, and for convenience, reference is Thus, the pre- 'mer is frequently used to indicate the polymerized product derived from a monomer in which the polymer has the-same identical composition as the monomer. In the present instance, however, polymerization involves the splitting and loss of water so that the process is essentially self-esterification. Thus, strictly speaking, the polymeric compounds are not absolutely polymers of the monomeric compounds, but since, for all practical purposes, they can be so indicated, and since such practice is common in the arts concerned with materials of this type, it is so adopted here. Thus, reference in the appended claims to polymers is intended to include the self-esterification products of the monomeric compounds.

In view of what has been said, and in view of the recognized hydrophile roperties of the remade to U. S. Patent No.'2,264,759, dated Decemher 2, 1941, to Paul C. Jones.

Referring again to the last two formulas indicating the compounds under consideration, it can be readily understood that such compounds,

- monium radical, etc.

curring oxyalkylene linkages, particularly the oxyethylene linkage, it is apparent that the materials herein contemplated may vary from compounds which are clearly water-soluble through self-emulsifying oils, to materials which 'are balsam-like and sub-resinous or semiresinous in nature. The compounds may vary from monomers to polymers, in which the unitary structure appears a number of times, for instance, 10 or 12 times. It is to be noted that true resins, il e., truly insoluble materials of a hard plastic nature, are not herein included. In other words, the polymerized compounds are soluble to a fairly definite extent, for instance, at least 5% in some solvents, such as water, alcohol, benzene, dichloroethyl ether, acetone, cresylic acid, acetic acid, ethyl acetate, dioxane or the like. This is simply another way of stating that the polymerized product contemplated must be of the sub-resinous type, which is commonly referred to as an A resin, or a B resin, as distinguished from a C resin, which is a highly infusible, insoluble resin (see Ellis, Chemistry of Synthetic Resins (1935), pages 862, et seq.).

Reviewing the form as presented, it is obvious that one may obtain compounds within the scope disclosed, which contain neither a free hydroxyl nor a free carboxyl group, and one may also obtain a compound of the type in which there is present at least one free carboxyl, or at least, one free hydroxyl, or both. The word polar has sometimes been used in the arts in this particular sense to indicate the presence of at least one free hydroxyl-group, or at least, one free carboxyl group, or both. In the case of the free carboxyl group, the carboxylic hydrogen atom may, of course, be replaced by any ionizable hydrogen atom equivalent, such, for example, as a metal, an ammonium radical, a substituted am- In the hereto appended claims the word polar is used in this specific sense.

We are aware that compounds similar to those contemplated in the present instance may be derived from polyhydroxylated compounds havin numerous instances, have the property of polyfunctionality. In view of this fact, where thereis at least one residual carboxyl and at least one residual hydroxyl, one would expect that under suitable conditions, instead of obstance, they may be derived from acyclic diglycerol, triglycerol, tetraglycerol, mixed polyglycerols, mannitol, sorbitol, various hexitols, dulcitol, pentaerythritol, sorbitan, mannitan, dipentaerythritol monoether, and other similar compounds. Such particular types in which higher hydroxylated materials are subjected to oxyalkylation and adipic acid. For purposes of brevity, the bulk of assists may be employed. Furthermore,

include the type in which there is an amino or amido nitrogen atom, particularly, when present in a low molal type of compound prior to oxyalkylation, reference being made to polyhydroxylated materials, including those having two or three hydroxyl groups, as well as those having more than three hydroxyl groups. For instance, the oxyalkylated derivatives, particularly the oxyethylated derivatives of ethyldiethanolamine, bis(hydroxyethyl) acetamide, the acetamide oi tris(hydroxymethyl) aminomethane,- tetrahydroxylated ethylene diamine, etc. Compounds may also be derived from cyclic diglycerol and the like. Furthermore, for convenience, attention is di-,

rected to a somewhat similar class of materials which are described in our application Serial No. 401,378, filed July 7, 1941, which subsequently matured as U. S. Patent No. 2,324,490, dated July 20, 1943. Said application involves the use of the same type of alcoholic bodies for reactants, but is limited,' among other things, to the compounds which are essentially symmetrical in nature, for instance, involving'the introduction of two alcoholic residues, whereas, in the present instance, one, two, or three, or more, might be introduced.

As indicated previously, the polybasic acids employed are limited to the type having not more than eight carbon atoms, for example, oxalic, malonic, succinic, glutaric, adipic, maleic, and phthalic. Similarly, one may employ acids such as fumaric, glutaconic, and various others, such as citric, malic, tartaric, and-the like. The selection of the particular tribasic or dibasic acid employed, is usually concerned largely with the convenience of manufacture of the finished ester,-and also the price of the reactants. Generally speaking, phthalic acid or anhydride tends to produce resinous materials, and greater care must be employed if theultimate or final product be of a sub-resinous type. Specifically, the preferred typeof polybasic acid is such as to contain six carbon atoms or less. Generally speaking, the higher the temperature employed, the easier it is to obtain large yields of esterifled product, ai-' though polymerization may be stimulated. Oxalic acid may be comparatively cheap, but it decomposes readily at slightly above the boiling point of water. For this reason it is more desir-v able touse an acid which is more resistant to pyrolysis. Similarly, when a polybasic acid is available in the form of an anhydride, such anhydride is apt to produce the ester with greater case than the acid itself. For this reason, maleic anhydride is particularly adaptable, and also, everything else considered, the cost is comparatively low on a per molar basis even though somewhat higher on a per pound basis. Succinic acid or the anhydride has many attractive qualities of maleic anlrvdride, and this is also true of hydroxyl group. I

The oxyalkylation of, glycerol is a well known the examples, hereinafter illustrated, will refer to the use of maleic anhydride, although it is understood that any other suitable reference is made to derivatives obtained by oxyethylation,

although, as previously pointed out, other oxyalkylating agents may be employed.

' As far as the range of oxyethylated glycerols employed as reactants is concerned, it is our preference to employ those in which approximately to 24 oxyethylene groups have been introduced into a single glycerol molecule. This means that approximately 5 to 8 oxyethylene radicals have been introduced for each original procedure (see Example 11 of German Patent No. 605,973, dated November 22, 1934, to I. G. Farbenindustrie A. G.) The procedure indicated in the following three examples is substantially identical with that outlined in said aforementioned German patent.

OXYETHYLATED GLYCEROL Example 1 184 pounds of glycerol are mixed with by weight, of caustic soda solution having a specific gravity of 1.383. The caustic soda acts as a catalyst. The ethylene oxide is added in relatively small amounts, for instance, about44 pounds at a time. The temperature employed is from 150-180 C. Generally speaking, the gauge pressure during the operation approximates 200 pounds at the maximum, and when reaction is completed, drops to zero, due to complete absorption of the ethylene oxide. when all the ethylene oxide has been absorbed and the re.

actants cooled, a second small portion, for instance, 44 more pounds of ethylene oxide, are added and the procedure repeated until the desired ratio of 15 pound moles of ethylene oxide to one pound mole of glycerol is obtained. This represents 660 pounds of ethylene oxide for 92 pounds of glycerol.

OxYErHYLArsn GLYCEROL Example 2 i The ratio of ethylene oxide is increased to 21 pound moles foreach pound mole of glycerol.

Otherwise, the same procedure is followed as'in I Example 1, preceding.

OXYETHYLATED GLYcEsoL Example 3 The same procedure is followed as in the two previous examples, except that the ratio of ethylene oxide to glycerol is increased to 21 to 1.

OXYETHYLA'I'ED GLYCEROL Marmara Example. 1

One pound mole of oxyethylated glycerol (1 to 15 ratio) prepared in the manner previously described is treated withone pound mole of maleic anhydride and heated at approximately C.

for approximately 30 minutes to 2 hours, with ceding example, except that: 2 moles of maleic' anhydride are employed so as to obtain the dimaleate instead of the monomaleate.

polybasic acid oxvmmm GLYCEROL MALE/ATE Ewample 3 The same procedure is followed as in the two preceding examples, except that 3 moles of maleic anhydride are employed so as to obtain the trimaleate.

OXYETHYLATED GLYCEROL MALEATEY Example 4 OXYETHYLATED GLYCEROL MALEATE Example 5 The same procedure is employed as in the preceding examples, except that oxyethylated glycerol (ratio 1 to 21) is employed instead of oxyethylated glycerol (ratio 1 to 15) or (1 to 18).

Previous reference has been made .to an alcoholic body which has been defined generically by the formula R1(OH)m. The sub-generic class of alcoholic compounds employed as reactants in the manufacture of the present compounds, are basic hydroxylated acylated. polyamino compounds free from ether linkages. Such materials are described inter alia in U. S. Patent No. 2,243,329, dated May 27, 1941, to De Groote and Blair. For instance, this particular patent describes a basic type acylated polyamine of thefollowing formula:

2 z \N C ..H2n (C n ZnNZ) :N/

in which n represents a small whole number varying from 2 to'lO; a: is a small whole number varying from 1 to 10; Z is a member of the class consisting of H, RCO, RCO, and D, in which RCOrepresents an acyl radical derived from a higher molecular weight carboxy acid; R'CO is an acyl radical derived from a lower molecular weight carboxy acid having 6 carbon atoms or less; and D is a member of the class consisting of alkyl, hydroxyalkyl, aminoalkyl, and acyloxyalkylene, in which instance the acyl group is a member of the class consisting of RC0 and R'CO;

radical, such as would be the case when the radical is derived from lactic acid; and

(d) The amines above described may be considered as derivatives of dichloralkanes or alkylene dichlorides. This is discussed clearly in the aforementioned De Groo'te and Blair patent. If such amines, which are derivatives ofpropylene dichloride, as indicated by the following composition:

tint

are, in turn, derived from glycerol dichlorhydrin (betahydroxy propylene dichloride) of the following composition: 1

equivalent, for the reasons stated.

and the acylated polyamine is further characterized by the fact that there must be present a member of the class consisting of (a) acyloxyalkylene radical in which the acyl group is RC0; and (b) joint occurrence of an amido radical in which the acyl group is RC0 and a hydroxyalkyl radical.

Needless to say, compounds of the kind therein described may be derived from polyamines having only two amino nitrogen atoms, as diiferentiated from polyamines having 3 amino nitrogen atoms or more. Thus, in the above formula, 1: may represent zero, as well as the numerals 1 to 10. It is obvious that numerous examples of the compounds indicated by the above formula are hydroxylated, due to the presence of one or more hydroxylated radicals of the following types:

((1) There may be present a hydroxyethyl group or a hydroxypropyl group or the like;

(12) The acyl group of the higher molecular weight carboxy acid may contain a hydroxyl group, as, for example, ricinoleic acid, hydroxystearic acid, etc.;

(c) The low molecular weight carboxy acid present may have a hydroxyl group in the acyl Although in the compounds above described the radical RCO may be derived from a higher molecular weight carboxy acid, in the present instance the invention is concerned with the particular type, in which RC0 is derived from a more narrow class, to wit, detergent-forming monocarboxy acids.

It is well known that certain monocarboxy organic acids containing 8 carbon atoms or more, and not more than 32 carbon atoms, are characterized by the fact that they combine with alkalies to produce soap or soap-like materials. These detergent-forming acids include fatty acids, resin acids, petroleum acids, etc. For the sake of convenience, these acids will be indicated by the formula R.COOH. Certain derivatives of detergentforming acids react with alkali to produce soapor soap-like materials, and are the obvious equivalent of the unchanged or unmodified detergentforming acids, for instance, instead of fatty acids, one might employ the chlorinated fatty acidfs. Instead of the resin acids, one might employ the hydrogenated resin acids. Instead of naphthenic acids, one might employ brominated naphthenic acids, etc.

The fatty acids are of the type commonly referred to as higher fatty acids; and of course, this is also true in regard to derivatives of the kind indicated, insofar that such derivatives are obtained from higher fatty'acids. The petroleum acids include not only naturally-occurring naphthenic acids, but also acids obtained by the oxidation of wax, paraffin, etc. Such acids may have as many as 32 carbon atoms. For instance, see U. S. Patent No. 2,242,837, dated May 20, 1941, to Shields.

We have found that the new composition of matter herein contemplated which is most valuable ,as a demulsifier, is preferably derived from unsaturated fatty acids having 18 carbon atoms.

- patent, it

tained from hydrolysis of cottonseed oil, soyabean oil, etc. Our preferred demulsifier is obtained from unsaturated fatty acids, and more specially, unsaturated fatty acids containing a hydroxyl radical, or unsaturated fatty acids, which have -been'subjected to an oxidation or oxyalkylation step, such as oxyethylation. Of the various unsaturated fatty acids, our choice is the hydroxylated type, to wit, ricinoleic acid.

For purposes of brevity, the bulk of any subsequent description will be concerned with fatty acids, and particularly unsaturated fatty acids.

. Further reference to other detergent-type monocarb'oxy acids is quite limited; but attention is directed to the. fact that an adequate description is found in the aforementioned'De Groote and Blairpatent. The following examples are substantially as they appear in said patent. One must not forget, however, that in addition to the 'amines described in said patent as reactants, one

can also use reagents such as ethylene diamine,

' bis(hydroxyethyl)ethylene diamine and tris(hydroxyethyl) ethylene diamine.

In view of what is said in the aforementioned De Groote and Blair will be obvious why the description of the amide is given as a primary raw material.

Amer:

Example 1 283'parts of stearic acid amide are heated with 438 parts'of triethylene tetramine for 10 about 130 C. until a test portion is soluble in diluted hydrochloric acid; at the end of the reac-' tion the pressure is preferably lowered to about 15 mm. Hg. Thereby 380 parts of a product probably corresponding to the formula C1'1H35CO.NH(C2H4NH) 2C2H4NH2 (monostearyl triethylene tetramine) are obtained.

Armin Example 2 281 parts of 01cm acid amide yield with 584 parts of triethylene tetramine, when heated for 10 hours to about 130 C., 400 parts of a product which is soluble in diluted hydrochloric acid, and probably corresponds to the monooleyl triethylene tetramine.

. Armin Example 3 283 parts of stearic acid amide are heated, in the same way as described in Examples 1 and 2 with 400 parts of a mixture of polyalkylene polyamines obtainable by heating ethylene dichloride with ammonia under pressure and removing any ethylene diamine formed during the latter reaction. After distilling an excess of basesiunder reduced pressure, 430 parts of a paste are obtained which is soluble in diluted acids.

AMIDE Example 4 300 parts of ricinoleic acid amide yield with 400' parts ofa mixture of bases according to Example 3, when heated to about 8 hours to 150-160 .C., 450 parts of a mixture of acylated bases which is easily soluble in diluted acetic orhydrochloric acid.

, Arum:

Example From 300 parts r ricinoleic acid amide and 400 Parts of a mixture of ,polyalkylenepolyamines, according to Examples 3 and 4, by heating for hours to i several hours to 150 C., simultaneously passing a current of dry air free from CO2, and finally re-. moving the excess of bases partly by distilling under reduced pressure and partly by washing with water, there are obtained 43 parts of a mixture of polyalkylene polyamines which is acylated y the radical or ricinoleic acid.

Amnr:

Example 6 100 parts by weight of olive oil and 100 parts by weight of diethylenetriamine are heated to about 180-200 C. until a test portion of the reaction mixture is soluble in dilute hydrochloric acid. After distilling off the excess of diethylenetriamine, advantageously under reduced pressure, there remains a strongly viscous mass, the hydrochloric acid solution of which has great foamforming properties.

A similar product is obtainable by heating free oleic acid with a large excess of diethylenetriamine under the same conditions.

' I AMIDE Example 7 310 parts by weight of the ethylester of oleic acid are heated with 286 parts by weight of tri- I Example 8 200' parts by weight of olive oil are heated at 180-200 C. with 300 parts by weight of a mixture ofbases, which is obtained by the action of ammonia on ethylene chloride at 120 C.Junder pressure or 10 atm., and after distilling off the ethylene diamine, said mixture of bases boiling at about 15 mm. mercury between and 300 C. Whena test portion of the reaction product is smoothly soluble in dilute hydrochloric acid, the water formed and the excess bases are distilled off under reduced pressure and a yellowish brown oil is obtained, a solution of which in dilute hydrochloric acid-can be used as a washing or wetting agent.

AMIDE Example 9 350 grams of monostearin and 300 grams of triethylene-tetramine are heated together at 180200 C. for 3 to 4 hour ,and then the displaced glycerine and the excess triethylene-. tetramine were washed out with water and the resulting product dried.

, Amnr:

Example 10 In the prior examples tetraethylene pentamine is substituted for the amines employed in the prior examples by using a suitable molecular equivalent, but without increasing the amount of fatty acid compound employed.

Amps

Example 11 Purified naphthenic acids derived from Gulf Coast crudes are employed in various examples preceding.

' Amnr:

Example 12 Carbpxy a idsderivedirom oxides oi Pennsylvania crude oil and having approximately -14 carbon atoms per mole ot'i'atty acid, are substituted in the Previous examples.

BAsrc TYPE OxYALxYLaTroN COMPOUND or Ammo Dmu'v TIva or PoLYArmwr:

Intermediate Earamplel I Materials of the kind described in Amide, Examples L-12,.. precedi,ng, are treated with one iii'ereoietliylene oxide in the manner previously described, so asto introduce oneoxyethyl radical.

'BAsIc TYPI OxYALxYLATIoN COMPOUND or Ammo DzaIvATIva or PoLYAmNr:

Intermediate Eirample 2 The same procedure is followed as in the preceding example, except that more than one oxyalkylgroup, or rather, oxyethyl group, is introduced, the preference being to introduce two orthree hyroxyethyl groups.

BASIC TYPE O'XYALKYLATION COMPOUND OF AMIDO DERIVATIVE OP POLYAmE Intermediate Erample s Propylene oxide is substituted for ethylene oxide in Examples 1 and 2, preceding.

BASIC TYPZOXYALKYLATION COMPOUND OF AMIDO DERIVATIVE OF POLYAMml Intermediate Example 4 Glycid is substituted for ethylene oxide in Examples 1 and 2, preceding.

OXYALKYLATI N DriuvATrvEs or POLYAMINE Example 1 OxYA xYLATIoN DERIVATIVES or PoLYAmNr: Example 2 Triethylene tetramine is substituted for diethylene triamine in Example 1.

OXYALKYLATION DERIvATIvss or PoLYAmNr:

. Example 3 Tetraethylene pentamine is substituted tor diethylene triamine in Example 1. 1

OxYA KvLATIoN DERIVATIVES or P'JLYAMINE Example 4 Pentaethylene hexamine is substiuted for diethylene triamine in Example 1.

BAsrc Trr: AcYLATIoN DzRIvATIvr: or

OxYALKYLATrm PoLYAmNn Intermediate Example '5 .A material ofthe kind described in Oxyalkylation Derivatives of Polyamine, Example 1, is-

- tained by such obtained in Amide Examples 1-12, previously described.

.BASIC TYPE ACYLATION DERIVATIVE 0F OXYALKYLATED POLYAMINI:

Intermediate Example 6 -A material of the kind described in Oxyalkylation Derivatives of Polyamine, Example 2, is acylated in the same manner in which amides are obtained in Amide Examples 1-12, previously described.

BASIC TYPE ACYLATION DERIVATIVE or OXYALKYLATED POLYAMINE Intermediate Example 7 A material of the kind described in Oxyalkylation Derivatives of Polyamine, Example 3, is acylated in the same manner in which amides are obtained in Amide Examples 1-12, previously described.

BAsIc TYPE AcYLATIoN DEiuvATIvE or OXYALKYLATED PoLYAmNs- Intermediate Example 8 BAsIc TYPE RE-ACYLATED OXYALKYLATION COM- POUND or Ammo DERIVATIVE 0F POLYAMINE Intermediate Example .9

Materials of the kind exemplified by Intermediates 1-4, preceding, which have been designated for convenience as Basic type oxyalkylation compound of amido derivative of polyamine, i. e., prepared by converting the polyamine into an amide and then subjecting the same to oxyalkylation, may, of course, be re-acylated, or acylated further, so as to introduce acyl groups of the kind described. Under such circumstances, one invariably obtains the mixed type, i. e., the esteramide type, provided that there has been total oxyalkylation. Excellent intermediates are obprocess, 1, e., the reacylation, or second acylation, of materials of the kind exemplified by Intermediates 1-4, inclusive, and particularly when such re-acylation takes place by means of detergent-forming acids, which, in the preferred form, are illustrated by fatty acids, and more particularly, by the hydroxylated fatty acid type. The preferred number of this type, in the present instance, as in other instances, is ricinoleic acid.

CouPLnTan MoNouzRIc DERIVATIVE Example 1 One pound mole of a product of the kind described under the heading Oxyethylated glycerol acylated in the .samemanner in which amides are .ample 1 and maleate, Example 1 is reacted with one pound mole of Basic type oxyalkyla'tion compound of amido derivative of polyamine, Intermediate Ex- Basic type oxyalkylation compound 01 amido derivative of polyamine, Intermediate Example 2, preferably in the absence of any high'boiling hydrocarbon or, inert solvent. However, if an inert vaporizing solvent is employed, it is generally necessary to use one which has a higher boiling range than xylene, and sometimes removal of such solvent might present a difllculty. In other instances, however, such high erol (ratio 1 to preceding.)

2,381,576 boiling inert vaporizing solvent, it employed,

Commune Monommrc DERIVATIVE Example 2 I The same procedure is followed as in-Completed monomeric derivative, Example 1, preceding, ex-v cept that the dimaleate described under the heading Oxyethylated glycerol 'maleate, Example 2 is used instead of the monomaleate.

COMPLETED Monounnrc DERIVATIVE Example 3 The same procedure is followed as in the two preceding examples, except that the trimaleate is substituted for the monomaleate or dimaleate in the two preceding examples.

Courtarnn Monomeric DERIVATIVE Example. 4

The same procedure is followed as in Examples 2 and 3, immediately preceding, except that for each pound mole of the maleate, or each pound mole of the trimaleate, instead of using one pound mole of an alcoholic compound of the kind described in Completed monomeric derivative, Example l, preceding, one employs two pound moles. COMPLETED MQNOMERIC Dearvmrrvs Example 5 The same procedure is followed as in Example 3, preceding, except that for each pound mole of trimaleate. instead of adding one pound mole of an alcoholic compound of the kind described, one adds three'pound moles of an alcoholic compound oi the kind described, in Completed monomeric derivative, Example 1, preceding, for reaction. a y

COMPLETED Monomeric Denver-rye Example 6 Reference to the preceding examples will show that in each and every instance oxyethylated glyc 15) has been employed as a raw material or primaryreactant. In the present instance, a more highly oxyethylated gylcerol is employed, to wit, one involving the ratio of l to 18. (See Oxyethylated glycerol COMPLETED Monomers Danrvarrvr Example 7 The same procedure is followed as in Example 6, immediately preceding, except that the exyethylated glycerol employed. represents one having an even higher'degree of oxyethylation. For exby the ratio of 1 to 21. (See maleate, Example 5, preample, one indicated Oxyethylated glycerol ceding.)

comrm'ran Monomnnrc DEar-vArrve Example 8 The same procedure is employed as in Examples glycerol maleate is of the kind described under Basic type acylation derivative of oxyalkylated polyamine, Intermediate Examples 5 to 8, inclusive.

Cournnrnn Monounnrc Dnnrvo'rrvn Example 9 The same procedure is followed as in Examples 1 to 7, preceding, except that the alcoholic body is one of the kind described previously under the heading Basic type re-acylated oxyalkylation compound of amido derivative of polyamine, Intermediate Example 9.

The method of producing such fractional esters is well known. The general procedure is to employ a temperature above the boiling point 01' water and below the pyrolytic point of the reactants. The products are mixed and stirred constantly during the heating and esteriflcation step.

If desired, an inert gas, such as dried nitrogen or dried. carbon dioxide, m'ay be passed through the mixture. Sometimes it is desirable to add an esterification catalyst, such as sulfuric acid, benzene sulfonic acid, or the like. i This is the same general procedure as employed in the manufacture of ethylene glycoldihydrogen diphthalate. (See U, S. Patent No. 2,075,107, dated March 30, 1937, to Frasier.)

Sometimes esterification is conducted mostreadily in the presence of an inert solvent, that carried away the water of esterification which may be formed, although as is readily appreciated, such water of esteriflcation is absent when such type of reaction involves an acid anhydride, such as maleic anhydride, and a glycol. However, if water is formed, for instance, when citric acid is employed, then a solvent such as xylene may be present and employed to carry off the water formed. The mixture of xylene vapors and water vapors can be condensed so that the water is separated. The xylene is then returned to the reaction vessel for further circulation. I

' This is a conventional and well known procedure maleate, Example 4,

and requires no further elaboration.

In the previous monomeric examples there is a definite tendency, in spite of precautions, at least in a number oi instances, to obtain polymeric materials and certain cogeneric by-products. This is typical, of course, of organic reactions of this kind, and as is well known, organic reactions per so are characterized by the fact that yields are the exception, rather than the rule, and that significantyields are satisfactory, especially in those instances where the lay-products or cogeners may satisfactorily serve with the same purpose as the principal or intentional product. This is true in the present instance. In

' many cases when the compound is manufactured 7 monomer.

scribed, partlcularly-a polymer whose molecular weight is a rather small multiple of the molecular weight of the monomer, for instance, a polymer whose. molecular weight is two, three, four, five, or six times the molecular weight of the Polymerization is hastened by the presence or an alkali, and thus, in instances where it is necessary to have a maximum yield of the monomer, it may be necessary to take such precautions that the alkali used in promoting oxyethylation of glycerol, be removed before subsequent reaction. This, of course, can be done in any simple manner by conversion to sodium chloride, sodium sulfate, or any suitable procedure.

In the preceding examples of the Completed 'acid, including alcohol acids, such as hydroxyacetic acid, lactic acid, ricinoleic acid and also polybasic acids of the kind herein contemplated.

With the above facts in mind, it becomes obvious that what has been previously said asto polymerization, with the" suggestion that byproducts or cogeneric materials were formed, may be recapitulated with greater definiteness, and one can readily appreciate that the formation of heat-rearranged derivatives or compounds must take place to a greater or lesser degree. Thus-the products herein contemplated may be characterized by being monomers of the type previously described, or esterification polymers, or the heat-rearranged derivatives of the same; and thus including the heat-rearranged derivatives of both the polymers and esterification monomers, separately and jointly. Although the class of materials specifically contemplated in this instance is a comparatively small and narrow class of a broad genus, yet it is obviously impossible to present any adequate formula which would contemplate the present series in their complete ramification, except in a manner employed in the hereto appended claims.

Although the products herein contemplated vary so broadly in their characteristics, i. e., monomers through sub-resinous polymers, soluble products, water-emulsifiable oils or compounds, hydrotropic materials, balsams, sub-resinous materials, semi-resinous materials, and the like, yet there is always present the characteristic unitary hydrophile structure related back to the oxyalkyl'ation, particularly the oxyethylation of the glycerol used as the raw material. When employed as a demulsifier, in the resolution of oil field emulsions, they may be added tothe emulsion atthe ratio of 1 part in 10,000, 1 part in 20,000, 1 part in 30,000, or for that matter, 1 part in 40,000. In such ratios it well may be that one cannot differentiate between the solubility of a compound completely soluble in water in any ratio, and a semi-resinous product apparently insoluble in water soluble materials are characterized. However, at such ratios the importance must reside in interfacial position and the ability to usurp, preempt, or replace the interfacial position previously occupied perhaps any event, reviewed in this light, the obvious common property runnin through the entire series, notwithstanding variation'in .molecular size and physical make-up, is absolutely apparent. Such statement is an obvious over-simplification of the rationale underlying demulsiflcation, and does not even consider the resistance of an interfacial flhn to crumbling, displacement, being forced into solution, altered wetability, and the like. As to amidification polymers, for instance, where Z is a polyamino amide radical, see what is said subsequently. 4

in ratios by which ordinary in.

by the emulsifying colloid. In

Consumes Pozmiuc DERIVATIVES INCLUDING HEAT-REARRANGED COGENERS Example 1 The monomer derived by reaction between one pound mole of an oxyethylated glycerol-dimaleate and one pound mole of an alcoholic body of the kind described under the heading Basic type oxyalkylation compound of amido derivatives of polyamine, Intermediate Example 2 is heated at a temperature of approximately 220-240 C., with constant stirring, for a period of 2-60 hours, so as to eliminate sufficient water to insure that the resultant product has a molecular weight of approximately twice that of the initial polymer.

Commune POLYMERIC DERIVATIVES INCLUDING "HEAT-Bummer!) COGENERS Example 2 COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERS Example 3 The same procedure is followed. as in Examples 1 and 2, preceding, except that the alcoholic body employed is of the kind described previously under the heading Basic type oxyalkylation compound of amido derivative of polyamine, Intermediate Example 3.

COMPLETED POLYMERIC DsnIvA'rIvEs INCLUDING HEAT-REARRANGED COGENERS Example 4 The same procedure is followed as in Examples 1 to '3, preceding, except that one polymerizes a mixture instead of a single monomer, for instance, a mixture of materials of the kind described in Completed monomeric derivative, Example 3, and in Completed monomeric derivative, Example 4, are mixed in molecular proportion and subjected to polymerization in the manner indicated in the previous examples.

It is understood, Of course, that the polymerized product need not be obtained as a result of a two-step procedure. In other words, ,pne need not convert the reactants into the polymer. The reactantsmay be converted through the monomer to the' polymer in one step. 'Indeed, the formation of themonomer and polymerization may take place simultaneously. This is especially' true if polymerization is conducted in the absence of an inert solvent, as previously described, and if one uses a comparatively higher temperature, for instance, approximately 220 C. for polymerization. Thus, one pound mole of oxyethylated glycerol polymaleate of the kind previously described is mixed with one pound mole of a material obtained by reaction between ricinoleic acid and triethylene-tetramine, followed by-introduction of at least two oxyethyl radicals. Such mixture is reacted for approximately thirty hours at about 220 C. until the mass is homogeneous. It isstirred constantly during reaction. Polyfunctionality may reside in dehydration '(etherization) of two hydroxyl groups attached to dissimilar molecules.-

The fact that the. powmerized and heat-rearranged productscan be mixed mechanically 2,226,119, dated December 2,233,383,-dated February and Keiser.

made in a single step, illustrates a phenomenon which sometimes occurs either in such instances where alcoholic bodies of the kind herein illustrated are contemplated as reactants, or where somewhat kindred alcoholic bodies are employed. The reactants may be to give a homogeneous mixture, or if the reactants do not mix to give a homogeneous mixture, then early in the reaction stage there is formed, to a greater or lesser de-v gree, suflicient monomeric materials, so that a homogeneous system is present. Subsequently,

as reaction continues, the system may become heterogeneous and exist in two distinct phases,

one being possibly in oily body of moderate viscosity, and the other being a heavier material, which is sticky or sub-resinous in nature. In many instances, it' will be found that the thinner liquid material is a monomer and the more viscous or resinous material is a polymer, as previously described. Such product can be used for demul'sification by adding a solvent which will mutually dissolve the two materials; or else, by separating the two heterogeneous phases and employing each as if it were reaction.

Materials of the kind herein contemplated may a separate product offlnd uses as wetting, detergent, and leveling agents in the laundry, textile, wetting agents and detergents in the acid washing of fruit, in the acid washing of buildingstone and brick; as a wetting agent and spreader in the application of asphaltin road building and the like, as a constituent of soldering flux preparations; as a flotation reagent in the flotation separation of various minerals; for flocculation and coagulation of various aqueous suspensions conemulsions of 'be used for other purposes, for instance, as a break inducer in doctor treatment of the kind intended to sweeten gasoline. (See U. S. Patent No. 2,157,223, dated May 9, 1939, to Sutton.)

Chemical compounds of the kind herein described are also of value as surface tension deare by no demulsiflers for water-inand dyeing industry; as

resinous, derivatives of carbon atoms, and D cognizance must be taken of the fact that the surface of the reacting vessel may increase or decrease reaction rate and degree of polymerizatio'n,-for instance, an iron reaction vessel speeds up reaction and polymerization, compared with a'glass-lined vessel.

As has been previously indicated, the sub-genus employed as an alcohol in the present instance is one of a series of alcoholic compounds which are contemplated in our co-pending applications Serial Nos. 497,118, 497,119, 497,120, 497,121,

and 497,135, all filed August 2, 1943.

Having thus described our invention, what we claim as new and desire to secure'by Letters Patent is:.

1. A member of the class consisting of suba hydroxylated acylated polyamine of the formula:

D DEN-T. (N.T) ,ND:

in which a: is a small numeral varying from o to T is an alkylene radical having from.2 to 10 is a memberof the class consisting of hydrogen atoms, alkyl radicals, hydroxyalkyl radicals, acyl radicals of the formula R200 and acyloxyalkylene radicals in which the acyl radical is R200, with the proviso that there must be present a member of the class consisting of:

- (a) An acyloxyalkylene radical in which the acyl radical is R200; and

(17) Joint occurrence of an amido radical in which the acyl radical is R200 and a hydroxy alkyl radical;

in all occurrences RZCO is a detergent-forming monocarboxy acyl radical having at least 8 and not more than 32 carbon atoms; the acyl radical substituted for a reactive hydroml hydrogen atom of said acylated basic hydrcxylated amine being the radical of an acidic fractional ester of the formula:

- [(RO)..'OOCR1COOZ],.

CaHi a [(RO),.'O0CR1CQOH],."'

in which -OCR1CO- is the acyl radical of a polycarboxy acid having not over 8 carbon atoms; Z represents a metallic cation; R-O is a member of the class consisting of ethylene oxide radicals, propylene oxide radicals, butylene oxide radicals and glycid radicals, and n represents a pressants 'in the acidization of calcareous oil- 1 bearing strata by means of strong mineral acid,

such as hydrochloric acid. Similarlmsgme members are efiective as surface tension depressants or wetting agents in the flooding of exhausted oilbearing strata.

As to using compounds of the kind herein de-, scribed as flooding agents for recovering oil from subterranean strata, reference is made to the proceduredescribed in detail in U. S. Patent No. 24, 1940, to De Groote and Keiser. As to using compounds of the kind herein described as demulsiflers, or in particular as surface tension depressants in combination with mineral acido'r acidization of oil-bearing strata, reference is made to U. S. atent No. 25, 1941, to De Groote numeral from 3 to 10, and n" represents the and n' represents the nuthat the sum of numeral 0, 1,-or 2, meral 1,2 or 3, with the proviso u +nIII 3.

2. The derivative described in claim 1', wherein R200 is a higher fatty acid having 18 carbon atoms. a

.3. The derivative described in claim 1, wherein RZCO is a higher fatty acid having is carbon atoms and at least one ethylene linkage.

4. The derivative described in claim 1, wherein RzCO is a higher fatty acid having is an ethylene radical. I 5. The derivative described in claim 1, wherein 'R2CO is a higher fatty acid having 18 carbon atoms and at least one ethylene linkage, and T I and R are ethylene radicals.

6. The derivative described in claim 1, wherein R200 is a higher fatty acid having 18 carbon atoms and at least one ethylene linkage, Tfand 18 carbon' atoms and at least one ethylene linkage, and T R are ethylene radicals, and the polycarboxy acid is a dibasic acid.

7. The derivative described in claim 1, wherein RzCO is a higher fatty acid having 18 carbon atoms and at least one ethylene linkage, T and R are ethylene radicals, and -OCR1CO-- is a maleic acid radical.

8. The derivative described in claim 1, wherein R2CO is a higher fatty acid having 18 carbon atoms and at least one ethylene linkage, T and R are ethylene radicals, and -OCR1CO-- is a phthalic acid radical. I

9. The derivative described in claim 1, wherein RzCO is a higher fatty acid having 18 carbon atoms and at least one ethylene linkage, T and R are ethylene radicals, and OCR1CO is an adipic acid radical.

10. The method of manufacturing compounds, defined in claim 1, by reacting a hydroxylated acylated polyamine of the formula:

in' which is is a small numeral varying from 0 to 5; T is an alkylene radical having from 2 to 10 carbon atoms, and D is a member of the class consisting of hydrogen atoms, alkyl radicals, hydroxyalkyl radicals, acyl radicals of the formula R200, and acyloxyalkylene radicals in which the'acyl radical is RaCO, with the proviso '(b) Joint, occurrence of class consisting of:

(a) An acyloxyalkylene radical in which the acyl radical is RzCO; and

an amido radical in which the acyl radical is RzCO, and hydroxy alkyl radical;

in all occurrences R2CO is a detergent-forming monocarboxy acyl radical having at least 8 and not more than 32 carbon atoms; with an acidic fractional ester of the formula:

in which OCR1C0 is the acyl radical of a polycarboxy acid having not over 8 carbon atoms; Z represents a metallic cation; R-O is a member of the class oxide radicals, propylene oxide radicals, butylene oxide radicals and glycid radicals, and n represents a numeral from 3 to 10, and n" represents the numeral 0, 1 or 2, and n' represents the numeral 1, 2 or 3, with the proviso that the sum of nll+ n!I! P.

MELVIN DE GROOTE.

BERNHARD KEISER.

consisting of ethylene 

